CN115387156A - Preparation method of silicon-based material antibacterial protective film - Google Patents
Preparation method of silicon-based material antibacterial protective film Download PDFInfo
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- CN115387156A CN115387156A CN202210850887.8A CN202210850887A CN115387156A CN 115387156 A CN115387156 A CN 115387156A CN 202210850887 A CN202210850887 A CN 202210850887A CN 115387156 A CN115387156 A CN 115387156A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/08—Filter paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/13—Silicon-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
Abstract
The invention provides a preparation method of a silicon-based material antibacterial protective film. The method comprises the steps of oxidizing and modifying the surface of the silicon-based material to form a surface antibacterial film, and then treating and fixing the antibacterial film by using a solution rich in amino long-chain compounds. In the surface oxidation modification, the epoxysilanization reagent is 3-Glycidoxypropyltrimethoxysilane (GPTMS), 3-Glycidoxypropyldimethylethoxysilane (GPDMES), 3- (2, 3) -epoxypropylmethyldimethoxysilane (GPDMMS) or 3- (2, 3) epoxypropoxypropyltrimethoxysilane (GPTS). The amino-rich long-chain compound comprises chitosanPolylysine, polyhistidine, polyethyleneimine or polyallylamine. The filter paper inoculated colibacillus (8099) provided by the invention has the density of 1.8 multiplied by 10 5 CFU/sample inoculated with Staphylococcus aureus (ATCC 6538) at a density of 1.9X 10 5 And (5) observing the number of bacteria cultured for 0h and 18h after CFU/sample, and calculating to obtain the antibacterial activity of more than 5.7 and the antibacterial rate of 99%.
Description
Technical Field
The invention relates to a preparation method of a protective film with antibacterial property, in particular to a preparation method of a silicon-based material antibacterial protective film.
Background
In the fully integrated molecular diagnostic analysis, the preservation of body fluid samples such as whole blood based on a silicon-based filter paper method is gradually developed and applied, however, in the application process, the body fluid samples preserved for a long time can cause the problem of bacterial reproduction. For example, when complex samples such as FTA blood cards and the like are stored for a long time, components such as a dry preservative need to be stored on filter paper fibers in advance, such operations increase the flow and difficulty of sample preparation and purification, and residual reagents also cause adverse effects on detection such as subsequent analysis and the like. The inorganic antibacterial agent comprises metal ion type and photocatalysis type, wherein the metal ion type comprises silver series, zinc series and copper series, and the antibacterial agent is prepared by fixing metals (or metal ions) such as silver, copper and zinc with antibacterial property on the surface of porous materials such as fluorite and silica gel by methods such as physical adsorption, ion exchange and the like; the photocatalysis type is mainly anatase type nano TiO 2 Its bactericidal power derives from its photocatalytic activity; the inorganic antibacterial agent has high cost and slow antibacterial effect, and the material is stable because the antibacterial film is fixed in an adsorption modeThe performance is poor. The organic antibacterial agents mainly comprise quaternary ammonium salts, organic silicon quaternary ammonium salts and the like, and mainly realize the bacteriostasis and sterilization effects on various bacteria, fungi and the like by virtue of cationic groups of the organic antibacterial agents, and the antibacterial agents selectively inhibit the combination of nucleic acid amplification polymerase and nucleic acid molecules, so that the amplification efficiency of the polymerase and the nucleic acid detection sensitivity are reduced. The natural antibacterial agent comprises chitin, chitosan, insect antibacterial protein and other animal extracts, has good biological reaction compatibility, but the direct coating modification mode can cause unstable antibacterial performance.
Therefore, it is necessary to provide a method for constructing a surface film of a silicon-based material, so as to satisfy the demand of people on improving the antibacterial property of the surface of the silicon-based material, and simultaneously ensure that the material has good biological reaction compatibility.
Disclosure of Invention
The invention aims to provide a modification process for improving the antibacterial property of a silicon-based material, and simultaneously has good nucleic acid analysis biocompatibility.
The invention is characterized in that the antibacterial property of the surface of the silicon-based fiber is improved. According to the method provided by the invention, the surface of the silicon-based material is activated through epoxy silane, and then the antibacterial coating film fixed on the surface of the silicon-based material is realized through long-chain graft copolymerization with amino.
The invention provides a preparation method of a silicon-based material antibacterial protective film, which comprises the following steps of treating the surface of a silicon-based material by using epoxy silane under a liquid phase condition; and treating the surface of the silicon-based material treated by the epoxy silane by using the amino long-chain compound-rich solution.
The epoxysilane includes: 3-glycidoxypropyltrimethoxysilane ((3-Glycidyloxypropyl) trimethoxysilane, GPTMS), 3-glycidoxypropyldimethylethoxysilane ((3-Glycidyloxypropyl) dimethylthiosilane, GPDMES), 3- (2, 3) -glycidoxypropylmethyldimethoxysilane ((3-Glycidyloxypropyl) dimethoxysilane, GPDMMS), or 3- (2, 3) glycidoxypropyltrimethoxysilane (3- (2, 3-Glycidoxypropyl) glycidyloxypropyltrimethoxysilane, GPTS).
The amino-rich long-chain compound comprises: chitosan, polylysine, polyhistidine, polyethyleneimine or polyallylamine.
The liquid phase is prepared from the epoxy silane, water, ethanol or isopropanol and contains 0.4-0.6% of the epoxy silane in percentage by mass.
The treatment with the epoxy silane comprises soaking for 20-30 h at 45-55 ℃ and shaking at the rotating speed of 115-125 rpm, then washing twice with water, ethanol or isopropanol, and airing at 20-30 ℃ or drying at 55-65 ℃.
The solution rich in the amino long-chain compound is a polymer solution with 0.05-0.5% of amino by mass percentage.
The treatment with the amino long-chain compound-rich solution comprises the following steps of using a PBS buffer solution which contains 0.020-0.030% of chitosan by mass, has a pH value of 4.5-5.5 and has a temperature of 4.5-55 ℃; in the buffer solution, shaking at the rotating speed of 115-125 rpm for 23-24 h to soak to realize covalent grafting with chitosan molecules, washing the filter paper by deionized water, and drying in an oven at 55-65 ℃.
The silicon-based material comprises filter paper/film containing silicon dioxide, organic silicon compounds and surface hydroxylation silicon base, quartz fiber, glass fiber, silicon resin, silicon rubber, silicon cellulose and polysilicic acid fiber.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
according to the technical scheme provided by the invention, the epoxy group of the epoxy silane and the compound with the amino group form covalent bonding, so that the obtained silicon-based material not only has good biocompatibility, but also has excellent bacteriostatic and antibacterial effects.
Drawings
FIG. 1 is a schematic view of the surface of an amino-modified antibacterial silicon-based fiber;
FIG. 2 is a nucleic acid amplification compatibility test.
Detailed Description
The silicon-based material with the antibacterial protection film is filter paper. The filter paper comprises filter paper or filter membrane made of glass fiber and quartz fiber. Unless otherwise stated, the concentrations in this specification are all characterized by mass percent.
Example 1, the silicon-based material with the antibacterial protective film was prepared as filter paper.
1) Surface epoxidation filter paper
Soaking filter paper in isopropanol (50 ℃) of GPTS (3- (2, 3) glycidoxypropyltrimethoxysilane and 3- (2, 3-Epoxypropoxy) propyltrimethoxysilane) with the concentration of 0.5 percent by mass under the condition of shaking at the speed of 120rpm for 24 hours, then cleaning the filter paper twice with the isopropanol, airing at 25 ℃ or drying at 60 ℃ to realize the epoxysilanization treatment on the surface of the filter paper, and obtaining the filter paper of the surface epoxysilanization antibacterial film.
2) Fixing the obtained surface epoxy silanization antibacterial film
Soaking the obtained filter paper of the surface epoxy silanization antibacterial film in PBS buffer solution with the chitosan concentration of 0.025% and the pH value of 5.0 at 50 ℃, shaking at the rotating speed of 120rpm for 24h to realize covalent grafting with chitosan molecules, washing the filter paper with deionized water, and drying in an oven at 60 ℃ to obtain the surface film cured antibacterial film filter paper shown in figure 1.
Example 2, the silicon-based material having the antibacterial protective film was prepared as filter paper.
1) Surface epoxidation filter paper
Soaking filter paper in isopropanol (50 ℃) of GPTS (3- (2, 3) glycidoxypropyltrimethoxysilane and 3- (2, 3-Epoxypropoxy) propylsilsesquioxane) with the concentration of 2.5 percent by mass for 16 hours under the condition of shaking at the speed of 120rpm, then cleaning the filter paper twice by using the isopropanol, airing the filter paper at 25 ℃ or drying the filter paper at 60 ℃ to realize epoxy group silanization treatment on the surface of the filter paper, and obtaining the filter paper of the epoxy group antibacterial silanization film on the surface.
2) And fixing the obtained surface epoxy silanization antibacterial film
Soaking the obtained filter paper with the surface epoxy silanized antibacterial film in PBS buffer solution with the chitosan concentration of 0.05% and the pH value of 5.0 at 50 ℃, shaking at the rotating speed of 120rpm for 24h to realize covalent grafting with chitosan molecules, washing the filter paper with deionized water, and drying in an oven at 60 ℃ to obtain the surface film cured antibacterial film filter paper shown in figure 1.
Example 3, the silicon-based material with the antibacterial protective film was prepared as filter paper.
1) Surface epoxidation filter paper
Soaking the filter paper in isopropanol (GPTMS (3-glycidoxypropyltrimethoxysilane) (3-Glycidyloxypropyl) trimethoxysilane) with the concentration of 5 percent by mass at 50 ℃ for 24 hours under the condition of shaking at the speed of 120rpm, then cleaning twice with the isopropanol, airing at 25 ℃ or drying at 60 ℃ to realize the epoxysilanization treatment on the surface of the filter paper, and obtaining the filter paper of the epoxysilanization antibacterial film on the surface.
2) And fixing the obtained surface epoxy silanization antibacterial film
Soaking the obtained filter paper of the surface epoxy silanization antibacterial film in PBS buffer solution with the chitosan concentration of 0.05 percent and the pH value of 5.0 at 50 ℃, shaking the filter paper at the rotating speed of 120rpm for 24 hours to realize covalent grafting with chitosan molecules, washing the filter paper with deionized water, and drying the filter paper in an oven at 60 ℃ to obtain the surface film cured antibacterial film filter paper shown in figure 1.
Example 4, the silicon-based material with the antibacterial protective film was prepared as filter paper.
1) Surface epoxidation filter paper
Soaking the filter paper in 0.5% by mass of GPTMS (3-glycidoxypropyltrimethoxysilane) (3-Glycidyloxypropyl) trimethoxysilane) ethanol at 50 ℃ for 24h under the condition of shaking at the speed of 120rpm, then washing with ethanol twice, airing at 25 ℃ or drying at 60 ℃ to realize the epoxysilanization treatment on the surface of the filter paper, and obtaining the filter paper of the surface epoxysilanization antibacterial film.
2) Fixing the obtained surface epoxy silanization antibacterial film
Soaking the obtained filter paper with the surface epoxy silanized antibacterial film in PBS buffer solution with the chitosan concentration of 0.05% and the pH value of 5.0 at 50 ℃, shaking at the rotating speed of 120rpm for 24h to realize covalent grafting with chitosan molecules, washing the filter paper with deionized water, and drying in an oven at 60 ℃ to obtain the surface film cured antibacterial film filter paper shown in figure 1.
Example 5, the silicon-based material with the antibacterial protective film was prepared as filter paper.
1) Surface epoxidation filter paper
Soaking the filter paper in 2 mass percent of GPTS (3- (2, 3) glycidoxypropyltrimethoxysilane, 3- (2, 3-Epoxypropoxy) propylsilsesquioxane) ethanol at 50 ℃ for 24 hours under the condition of shaking at the speed of 120rpm, then cleaning twice with ethanol, airing at 25 ℃ or drying at 60 ℃ to realize epoxy group silanization treatment on the surface of the filter paper, and obtaining the filter paper of the epoxy group silanized antibacterial film on the surface.
2) Fixing the obtained surface epoxy silanization antibacterial film
Soaking the obtained filter paper with the surface epoxy silanized antibacterial film in PBS buffer solution with the chitosan concentration of 0.025% and the pH value of 5.0 at 50 ℃, shaking at the rotating speed of 120rpm for 24h to realize covalent grafting with chitosan molecules, washing the filter paper with deionized water, and drying in an oven at 60 ℃ to obtain the surface film cured antibacterial film filter paper shown in figure 1.
The antibacterial property of the quartz fiber filter paper prepared by the invention is detected.
The antibacterial property of the filter paper is detected according to GB/T20944.2-2007 evaluation of antibacterial property of textiles, part 2 absorption method. Cutting quartz fiber filter paper and standard cotton cloth into two patterns with sizes of 18mm × 18mm and the same specification, inoculating Escherichia coli (8099) with density of 1.8 × 10 5 CFU/sample inoculated with Staphylococcus aureus (ATCC 6538) at a density of 1.9X 10 5 And (5) observing the number of bacteria cultured for 0h and 18h in the CFU/sample, and respectively calculating the bacteriostatic activity value and the bacteriostatic rate of the two samples. The results are shown in table 1 below:
TABLE 1 bacteriostatic activity and bacteriostatic rate of the silicon-based material filter papers of examples 1 to 5 of the present invention and the existing standard cloth
The detection result shows that the antibacterial property of the patterns prepared in the embodiments 1 and 2 of the invention to escherichia coli and staphylococcus aureus can reach more than 97%; examples 3, 4, 5 have > 99% antibacterial activity against E.coli and Staphylococcus aureus.
The filter paper preparation method of examples 6-10 is the same as that of example 1, but the epoxy group silanization reagent used is different from the amino group-rich long chain compound, and the effects are respectively shown in the following table 2:
TABLE 2 bacteriostatic activity and bacteriostatic rate of the silicon-based material filter papers of examples 6 to 10 of the present invention
Remarking: GPTMS (3-glycidoxypropyltrimethoxysilane, (3-Glycidoxypropyl) trimethyoxysilane), GPDMES (3-glycidoxypropyldimethylethoxysilane, (3-Glycidoxypropyl) dimethyoxysilane), GPDMMS (3- (2, 3) -glycidylmethyldimethoxysilane,
(3-Glycidoxypropyl) dimethoxymet-hylsilane), GPTS (3- (2, 3) glycidoxypropyltrimethoxysilane,
3-(2,3-Epoxypropoxy)propyltrimethoxysilane)
and detecting the nucleic acid amplification compatibility of the silicon-based fiber filter paper prepared by the invention.
The invention uses PCR (Real-time Quantitative Polymerase Chain Reaction) to quantitatively analyze the biocompatibility of the obtained filter material. In a PCR system, an excessive amount of SYBR fluorescent dye is added, a fluorescent signal is emitted after the SYBR fluorescent dye is specifically doped into a DNA double strand, and molecules which are not doped with the SYBR fluorescent dye in the strand do not emit any fluorescent signal, so that the increase of the fluorescent signal is completely synchronous with the increase of a PCR product. The difference of the biocompatibility of PCR amplification among materials is compared by taking the number of cycles of the fluorescence signal in the reaction tube to a set Cycle threshold (Ct value) as a standard.
The polymerase chain reaction system included 0.425. Mu.L each of a pair of primers (10. Mu.M), 12.5. Mu.L of Power 2 × SYBR real-time PCR premix (BioTeke) and 0.125. Mu.L of 50. Mu.g/. Mu.L BSA, and 11.525. Mu.L deionized water.
The following table 3 shows the Ct values (after 1ng of standard nucleic acid amplification) of the filter paper of examples 1 to 10, the non-modified silica-based fiber filter paper, and the non-silica-based fiber filter paper of the present invention.
TABLE 3 Ct values of the filter papers of examples 1 to 10 of the present invention, the unmodified silica-based fiber filter papers, and the silica-based fiber filter papers
As can be seen from FIG. 2, the silicon-based fiber filter paper modified by the present invention has good biocompatibility for PCR extension, and taking the Ct value after amplification of 1ng of standard nucleic acid as an example, the Δ Ct =1.9 of the group of unmodified silicon-based fiber filter paper and silicon-free fiber filter paper, i.e., the amplification efficiency of unmodified silicon-based fiber is only 1/2 of that of silicon-free fiber filter paper 1.9 X 100% =27%, and the delta Ct of the filter paper of the examples 1 to 10 is 0.01 to 0.65 compared with the filter paper group without the silicon-based fiber, and the amplification efficiency is between 64 and 99 percent.
The result shows that the modified material has obvious advantages in the biocompatibility of the nucleic acid amplification polymer enzyme.
Finally, it should be noted that: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (7)
1. The preparation method of the antibacterial protective film of the silicon-based material is characterized by comprising the following steps of treating the surface of the silicon-based material with epoxy silane under a liquid phase condition; and treating the surface of the silicon-based material treated by the epoxy silane by using the amino long-chain compound-rich solution.
2. A method for producing an antibacterial protective film on a silicon-based material according to claim 1,
the epoxysilane includes: 3-glycidoxypropyltrimethoxysilane ((3-Glycidyloxypropyl) trimethyoxysilane, GPTMS), 3-glycidoxypropyldimethylethoxysilane ((3-Glycidyloxypropyl) dimethyoxysilane, GPDMES), 3- (2, 3) -glycidyloxypropylmethyldimethoxysilane ((3-Glycidyloxypropyl) dimethyoxysilane, GPDMMS), or 3- (2, 3) glycidoxypropyltrimethoxysilane (3- (2, 3-Glycidyloxypropyl) pyridylmethoxysilane, GPTS);
the amino-rich long-chain compound comprises: chitosan, polylysine, polyhistidine, polyethyleneimine or polyallylamine.
3. The method for producing an antibacterial protective film on a silicon substrate according to claim 1, wherein said liquid phase is a liquid phase prepared from said epoxysilane, water, ethanol or isopropyl alcohol, and contains 0.4 to 0.6% by mass of said epoxysilane.
4. The method for preparing an antibacterial protective film on a silicon-based material according to claim 1, wherein the treatment with the epoxysilane comprises soaking the silicon-based material at 45-55 ℃ for 20-30 hours while shaking at 115-125 rpm, washing with water, ethanol or isopropanol twice, and air-drying at 20-30 ℃ or oven-drying at 55-65 ℃.
5. The method for producing an antibacterial protective film on a silicon-based material according to claim 1, wherein the amino long-chain compound-rich solution is a polymer solution containing an amino group at a concentration of 0.05 to 0.5% by mass.
6. The method for producing an antibacterial protective film on a silicon-based material according to claim 1, wherein said treatment with the amino group-rich long-chain compound solution comprises subjecting the amino group-rich long-chain compound solution to a PBS buffer solution containing 0.020 to 0.030% by mass of chitosan and having a pH of 4.5 to 5.5 and a temperature of 4.5 to 55 ℃; in the buffer solution, shaking at the rotating speed of 115-125 rpm for 23-24 h to soak to realize covalent grafting with chitosan molecules, washing the filter paper by deionized water, and drying in an oven at 55-65 ℃.
7. The method for producing an antibacterial protective film on a silicon-based material according to claim 1, wherein the silicon-based material comprises a filter paper/film containing silicon dioxide, an organosilicon compound and a surface-hydroxylatable silicon base, quartz fiber, glass fiber, silicone resin, silicone rubber, silicone cellulose and polysilicic acid fiber.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090215124A1 (en) * | 2005-02-15 | 2009-08-27 | Weidong Cao | Nucleic acid isolation methods and materials and devices thereof |
| CN101643321A (en) * | 2009-09-01 | 2010-02-10 | 博奥生物有限公司 | High-polymer three-dimensional amino-group substrate as well as preparation method and application thereof |
| JP2010259405A (en) * | 2009-05-11 | 2010-11-18 | Gunma Univ | Nucleic acid-immobilized carrier and utilization of the same |
| CN108085314A (en) * | 2016-11-21 | 2018-05-29 | 清华大学 | A kind of amination filter paper/film purified for nucleic acid extraction and preparation method and application |
| CN110193090A (en) * | 2019-05-31 | 2019-09-03 | 盐城工学院 | A kind of preparation method of the bacteria cellulose dressing with antibacterial bacteriostatic function |
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2022
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090215124A1 (en) * | 2005-02-15 | 2009-08-27 | Weidong Cao | Nucleic acid isolation methods and materials and devices thereof |
| JP2010259405A (en) * | 2009-05-11 | 2010-11-18 | Gunma Univ | Nucleic acid-immobilized carrier and utilization of the same |
| CN101643321A (en) * | 2009-09-01 | 2010-02-10 | 博奥生物有限公司 | High-polymer three-dimensional amino-group substrate as well as preparation method and application thereof |
| CN108085314A (en) * | 2016-11-21 | 2018-05-29 | 清华大学 | A kind of amination filter paper/film purified for nucleic acid extraction and preparation method and application |
| CN110193090A (en) * | 2019-05-31 | 2019-09-03 | 盐城工学院 | A kind of preparation method of the bacteria cellulose dressing with antibacterial bacteriostatic function |
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